US8420001B2 - Influencing specific mechanical properties of three-dimensional objects manufactured by a selective sintering by means of electromagnetic radiation from a powder comprising at least one polymer or copolymer - Google Patents

Influencing specific mechanical properties of three-dimensional objects manufactured by a selective sintering by means of electromagnetic radiation from a powder comprising at least one polymer or copolymer Download PDF

Info

Publication number
US8420001B2
US8420001B2 US12/454,473 US45447309A US8420001B2 US 8420001 B2 US8420001 B2 US 8420001B2 US 45447309 A US45447309 A US 45447309A US 8420001 B2 US8420001 B2 US 8420001B2
Authority
US
United States
Prior art keywords
polymer
powder
dimensional object
copolymer
mpa
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active, expires
Application number
US12/454,473
Other languages
English (en)
Other versions
US20090312454A1 (en
Inventor
Martin Leuterer
Andreas Pfister
Frank Mueller
Alan Wood
Brian Wilson
Horst Sandner
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
EOS GmbH
Original Assignee
EOS GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=40040161&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=US8420001(B2) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by EOS GmbH filed Critical EOS GmbH
Priority to US12/454,473 priority Critical patent/US8420001B2/en
Assigned to EOS GMBH ELECTRO OPTICAL SYSTEMS reassignment EOS GMBH ELECTRO OPTICAL SYSTEMS ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: WILSON, BRIAN, WOOD, ALAN, Sandner, Horst, LEUTERER, MARTIN, MUELLER, FRANK, PFISTER, ANDREAS
Publication of US20090312454A1 publication Critical patent/US20090312454A1/en
Application granted granted Critical
Publication of US8420001B2 publication Critical patent/US8420001B2/en
Active legal-status Critical Current
Adjusted expiration legal-status Critical

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
    • B29C35/16—Cooling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/10—Processes of additive manufacturing
    • B29C64/141—Processes of additive manufacturing using only solid materials
    • B29C64/153—Processes of additive manufacturing using only solid materials using layers of powder being selectively joined, e.g. by selective laser sintering or melting
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
    • B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
    • B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
    • B29C35/0805—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation
    • B29C2035/0838—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation using laser
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0037—Other properties
    • B29K2995/004—Semi-crystalline
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y10/00—Processes of additive manufacturing

Definitions

  • the present invention relates to a process for manufacturing a three-dimensional object from a powder by selective sintering by means of electromagnetic radiation of the powder, wherein the powder comprises at least one polymer material and wherein the manufactured three-dimensional object has an advantageously decreased crystallinity compared to conventional selective sintering by means of electromagnetic radiation. Furthermore, the present invention relates to a three-dimensional object obtained by said process, an apparatus for said process and a use of a preselected polymer powder in said process.
  • a process for manufacturing a three-dimensional object by a selective sintering by means of electromagnetic radiation may be carried out layer-wise with a source for electromagnetic radiation.
  • three-dimensional objects are manufactured in a layer-wise manner by applying layers of a powder and bonding them to each other by a selective solidification of the powders at positions in the layers corresponding to cross-sections of the objects.
  • FIG. 1 shows an example of a prior art laser sintering device by means of which a process for a layer-wise manufacturing of a three-dimensional object may be performed.
  • the device comprises a container 1 .
  • This container is open to the top and is limited at the bottom by a support 4 for supporting an object 3 to be formed.
  • a work plane 6 is defined.
  • the object is located on the top side of the support 4 and is formed from a plurality of layers of a building material in powder form that can be solidified by means of electromagnetic radiation, wherein the layers are in parallel to the top side of the support 4 .
  • the support may be moved in a vertical direction, i.e. in parallel to the sidewall of the container 1 , via a height adjustment device. Thereby the position of the support 4 relative to the work plane 6 can be adjusted.
  • an application device 10 is provided for applying the powder material 11 to be solidified onto the support surface 5 or a previously solidified layer.
  • an irradiation device in the form of a laser 7 which emits a directed light beam 8 , is arranged above the work plane 6 .
  • This light beam 8 is directed as deflected beam 8 ′ towards the work plane 6 by a deflection device 9 such as a rotating mirror.
  • a control unit 40 allows to control the support 4 , the application device 10 and the deflection device 9 .
  • the items 1 to 6, 10 and 11 are located within a machine frame 100 .
  • the powder material 11 is applied layer-wise onto the support 4 or a previously solidified layer and is solidified at the positions of each powder layer that correspond to the object by means of the laser beam 8 ′. After each selective solidification of a layer the support is lowered by the thickness of the powder layer to be subsequently applied.
  • the object of the present invention is to provide an improvement of a process for manufacturing a three-dimensional object by selective sintering by means of electromagnetic radiation of polymer powders, which leads to improved mechanical properties of the manufactured objects.
  • the present invention it has been surprisingly found that when observing that the manufactured three-dimensional objects have a specific range of crystallinity, a marked improvement of certain, very advantageous mechanical properties including, but not limited to high stiffness, high compression strength, high impact strength, high maximal tensile- and bending strength as well as high elongation at break and high heat deflection temperature are obtained, while on the other hand opposing or trade-off properties such as good chemical resistance and low post shrinkage by post crystallisation are well balanced. Furthermore, it has been surprisingly found that particular process conditions, especially regarding the cooling period after sintering, and particular selection criteria concerning preselected polymer materials, respectively alone or in combination, contribute to significant enhancements of the aforementioned mechanical properties and balancing characteristics.
  • the advantages of the invention are particularly feasible when polyaryletherketone polymer or a polyaryletherketone copolymer, or when a polyamide polymer or a polyamide copolymer is appropriately used as a polymer material of the polymer powder.
  • the advantages of the invention are also feasible for composites, wherein the crystallinity value relates to the polymer matrix of the composite.
  • Such composites comprise one or more filler(s) and/or additive(s) besides a matrix of the respective polymer, copolymer or blend.
  • the process according to the present invention can be carried out layer-wise in an additive process, wherein successive layers of the object to be formed from solidifiable powder material are subsequently solidified by the electromagnetic radiation at positions corresponding to the cross-section of the object.
  • a process for manufacturing a three-dimensional object from a powder by selective sintering by means of electromagnetic radiation of the powder wherein the powder comprises a preselected polymer or copolymer and is subjected to selective sintering such that the manufactured three-dimensional object has a final crystallinity which is in such a range that the balance of the overall mechanical properties of Young's modulus, tensile strength and elongation at break is improved.
  • the Young's modulus of the polymer or copolymer is preferably at least 500 MPa, more preferably at least 1000 MPa and particularly at least 2000 MPa, tensile strength is preferably at least 20 MPa, more preferably at least 30 MPa and particularly at least 40 MPa and elongation at break is preferably at least 1%, more preferably at least 2%, still more preferably at least 5%. and particularly at least 20%.
  • the Young's modulus is preferably at least 3000 MPa, more preferably at least 3500 MPa and particularly at least 4000 MPa, tensile strength is preferably at least 50 MPa, more preferably at least 70 MPa and particularly at least 90 MPa and elongation at break is preferably at least 1.5%, more preferably at least 2%, still more preferably at least 3%.
  • Young's modulus is preferably at least 1000 MPa, more preferably at least 1500 MPa, still more preferably at least 2500 MPa, tensile strength is preferably at least 35 MPa, more preferably at least 45 MPa and particularly at least 70 MPa and elongation at break is preferably at least 5%, more preferably at least 20%, still more preferably at least 40% and particularly at least 60%.
  • polymer or copolymer is selected from the group consisting of polyamide (PA), polyaryletherketone (PAEK), polyarylethersulfone (PAES), polyester, polyether, polyolefin, polystyrene, polyphenylenesulfide, polyvinylidenfluoride, polyphenylenoxide, polyimide and copolymers and blends comprising at least one of the aforementioned polymers.
  • PA polyamide
  • PAEK polyaryletherketone
  • PAES polyarylethersulfone
  • polymer or copolymer is selected from the group consisting of polyamide, polyaryletherketone, and copolymers and blends comprising at least one of the aforementioned polymers.
  • polymer or copolymer is a polyaryletherketone (PAEK) selected from the group consisting of polyetheretherketone (PEEK), polyetherketoneketone (PEKK), polyetherketone (PEK), polyetherketoneketone (PEEKK) and polyetherketoneetherketoneketone (PEKEKK) and Polyetheretherketone (PEEEK) and copolymers and blends comprising at least one of the aforementioned polymers.
  • PAEK polyaryletherketone
  • polymer or copolymer is a polyaryletherketone (PAEK) selected from the group of PEEK, PEK, PEKEKK, and copolymers and blends comprising at least one of the aforementioned polymers.
  • PAEK polyaryletherketone
  • copolymer is a polyaryletherketone (PAEK)/polyarylethersulfone(PAES)-copolymer.
  • polyaryletherketone(PAEK)/polyarylethersulfone(PAES)-copolymer is selected from the group consisting of polyaryletherketone(PAEK)/polyarylethersulfon(PAES)-diblock-copolymers or PAEK/PAES/PAEK-triblock-copolymers, preferably from the group consisting of (PEK)/(PES)-diblock-copolymers and PEK/PES/PEK-triblock-copolymers.
  • polyamide (PA) polymer or copolymer has at least one repeating unit of the backbone chain wherein the length of at least one aliphatic chain is in the range of preferably C4 to C18, more preferably C6 to C12 and particularly C10 to C12.
  • the Young's modulus of the polymer or copolymer is preferably at least 500 MPa, more preferably at least 1000 MPa and particularly at least 2000 MPa, tensile strength is preferably at least 20 MPa, more preferably at least 30 MPa and particularly at least 40 MPa and elongation at break is preferably at least 1%, more preferably at least 2%, still more preferably at least 5%. and particularly at least 20%.
  • the Young's modulus is preferably at least 3000 MPa, more preferably at least 3500 MPa and particularly at least 4000 MPa, tensile strength is preferably at least 50 MPa, more preferably at least 70 MPa and particularly at least 90 MPa and elongation at break is preferably at least 1.5%, more preferably at least 2%, still more preferably at least 3%.
  • Young's modulus is preferably at least 1000 MPa, more preferably at least 1500 MPa, still more preferably at least 2500 MPa, tensile strength is preferably at least 35 MPa, more preferably at least 45 MPa and particularly at least 70 MPa and elongation at break is preferably at least 5%, more preferably at least 20%, still more preferably at least 40% and particularly at least 60%.
  • the cooling step cools the object from a temperature which is 1-50° C., more preferably 1-30° C. and most preferably 1-10° C. lower than T m of the polymer or copolymer comprised by the powder down to T g of the polymer or copolymer comprised by the powder at a cooling rate of 0.01-10° C./min, preferably 0.1-5° C./min, more preferably 1-5° C./min, after completion of the object, wherein T m is the melting temperature and T g is the glass transition temperature of the polymer or copolymer comprised by the powder, respectively.
  • (40) A three-dimensional object obtained by a selective sintering of a polymer, a copolymer or a blend of polymers in powder form by means of electromagnetic radiation, wherein the final crystallinity is in such a range that the balance of the overall mechanical properties of Young's modulus, tensile strength and elongation at break is improved.
  • the Young's modulus of the polymer or copolymer is preferably at least 500 MPa, more preferably at least 1000 MPa and particularly at least 2000 MPa, tensile strength is preferably at least 20 MPa, more preferably at least 30 MPa and particularly at least 40 MPa, and elongation at break is preferably at least 1%, more preferably at least 2%, still more preferably at least 5%.
  • the Young's modulus is preferably at least 3000 MPa, more preferably at least 3500 MPa and particularly at least 4000 MPa, tensile strength is preferably at least 50 MPa, more preferably at least 70 MPa and particularly at least 90 MPa and elongation at break is preferably at least 1.5%, more preferably at least 2%, still more preferably at least 3%.
  • Young's modulus is preferably at least 1000 MPa, more preferably at least 1500 MPa, still more preferably at least 2500 MPa, tensile strength is preferably at least 35 MPa, more preferably at least 45 MPa and particularly at least 70 MPa and elongation at break is preferably at least 5%, more preferably at least 20%, still more preferably at least 40% and particularly at least 60%.
  • An apparatus for manufacturing a three-dimensional object from a powder by selective sintering by means of electromagnetic radiation of the powder comprising a temperature control device for a predefined cooling of the object after completion of manufacturing the object.
  • the Young's modulus of the polymer or copolymer is preferably at least 500 MPa, more preferably at least 1000 MPa and particularly at least 2000 MPa, tensile strength is preferably at least 20 MPa, more preferably at least 30 MPa and particularly at least 40 MPa and elongation at break is preferably at least 1%, more preferably at least 2%, still more preferably at least 5%. and particularly at least 20%.
  • the Young's modulus is preferably at least 3000 MPa, more preferably at least 3500 MPa and particularly at least 4000 MPa, tensile strength is preferably at least 50 MPa, more preferably at least 70 MPa and particularly at least 90 MPa and elongation at break is preferably at least 1.5%, more preferably at least 2%, still more preferably at least 3%.
  • Young's modulus is preferably at least 1000 MPa, more preferably at least 1500 MPa, still more preferably at least 2500 MPa, tensile strength is preferably at least 35 MPa, more preferably at least 45 MPa and particularly at least 70 MPa and elongation at break is preferably at least 5%, more preferably at least 20%, still more preferably at least 40% and particularly at least 60%.
  • FIG. 1 shows a laser sintering device for a layer-wise manufacturing of a three-dimensional object.
  • Objects manufactured by selective sintering by means of electromagnetic radiation of a powder comprising at least one polymer typically have crystallinity values substantially higher than objects manufactured by classical polymer processing technologies like e.g. injection molding. That is, in a process for manufacturing a three-dimensional object from a powder by selective sintering by means of electromagnetic radiation of the powder comprising at least one polymer, for example of a type as it is illustrated in FIG. 1 , crystallinity values in the manufactured object tend to become predominant without the crystallinity adjustment according to the present invention. Specifically, in the layer-wise building process, a high powder bed temperature lying at about 1-50° C., preferably 1-30° C., even more preferably 1-20° C. and most preferably 1-10° C.
  • the object is typically exposed to relatively high processing temperatures for a substantial period of time and still passes a usually very long cooling period.
  • the processing temperature should be kept close to the melting point of the polymer powder in order to provide for a good connection between successive layers and minimizes the formation of pores due to an inadequately melting of the powder particles. Consequently, the temperature of the powder bed is kept during the whole building process above the crystallization temperature T c of the polymer.
  • the generated object itself may be exposed for a long time to temperatures above T c .
  • the crystallinity in the manufactured object may be beneficially adjusted still high enough to also provide for positive influences on high chemical resistance, low post shrinkage at temperatures above Tg or high stiffness of the manufactured object.
  • an excellent balance of properties can be achieved by the present invention.
  • crystallinity of the object manufactured from polymer powder materials is properly limited and preferably adjusted within a particular range, a marked improvement of certain, very advantageous mechanical properties like tensile strength, Young's modulus and elongation at break can be attained.
  • 1) Preselecting an appropriate type of polymer material, 2) tailoring of the structural characteristics and/or modifications of the polymer comprised in the preselected powder, and/or 3) paying attention to a predefined and/or controlled cooling step after completion of the sintering process of the object are particularly effective and preferred means to limit and adjust the crystallinity values of the manufactured object.
  • a predefined and/or controlled cooling step after completion of the object after the sintering is preferably applied to the object.
  • the predefined and/or controlled cooling step may be realized by predefined slow cooling, possibly slower than native (passive) cooling, or by active cooling in order to provide fast cooling.
  • useful settings for said cooling step can be experimentally tested with the proviso that the final crystallinity is preferably 80% or less, preferably 50% or less, especially 5-70%, more preferably 15-50% and particularly 15-35%.
  • PEEK polyetheretherketone
  • PAEK polyetheretherketone
  • PEEK polyetheretherketone
  • PAEKs after the sintering/building process are: When the manufactured object is cooled from the processing temperature which is preferably at a temperature being 1-10° C.
  • the cooling rate is preferably 0.01-10° C./min and more preferably between 0.1-5° C./min and most preferably between 1-5° C./min, in order to minimize and ensure low post-crystallization and low curling of the parts.
  • a cooling rate e.g. 0.3° C./min
  • a low crystallinity of e.g. 36% is attained, which provides improved mechanical properties like a tensile strength of 79 MPa (see Example 5).
  • Further limiting crystallinity down to 31%, for example by applying a faster cooling rate of e.g. more than 0.3° C./min provides a surprisingly further improved tensile strength of 88 MPa (Example 6).
  • the cooling rate after completion of the object may also affect the curling and thus the dimensional stability of the object. It has been surprisingly found that the cooling rate can be predefined such that the three-dimensional object has not only a specific range of crystallinity and thereby provides the above mentioned advantageous mechanical properties, but also a high dimensional stability, that is, it does not curl.
  • a PEEK powder rather needs a relatively slow cooling rate, e.g. about 0.1-0.3° C./min, compared to a PEK powder in order to attain both low crystallinity and high dimensional stability (avoiding curling) (cf. Examples 2 and 3). At a higher cooling rate, this material would tend to curling phenomena.
  • Particularly suitable alternative polymer materials other than PEAK polymers and copolymers include, but are not limited to polyamides, polyesters, polyethers, polyolefins, polystyrenes, polyphenylensulfides, polyvinylidenfluorides, polyphenylenoxides, polyimides, and copolymers thereof.
  • Suitable polyamide polymers or copolymers may be selected from the group consisting of polyamide 6, polyamide 66, polyamide 11, polyamide 12, polyamide 612, polyamide 610, polyamide 1010, polyamide 1212 and copolymers comprising at least one of the aforementioned polymers, and polyamide elastomers such as polyether block amide, e.g. PEBAX®-based materials.
  • Suitable polyester polymers or copolymers may be selected from the group consisting of polyalkylentherephthalates (e.g. PET, PBT) and their copolymers with 1,4-cyclohexanedimethylol.
  • Suitable polyolefin polymers or copolymers may be selected from the group consisting of polyethylene and polypropylene.
  • Suitable polystyrene polymers or copolymers may be selected from the group consisting of syndiotactic- and isotactic polystyrene.
  • Examples 1 and 2 showing a lowering from 52% to 45%). While an increase in molecular weight might lower the density and thus increase porosity, it substantially contributes to increasing the tensile strength and elongation at break (see, e.g. Examples 1 and 2 showing a considerable increase in tensile strength from 44 MPa to 71 MPa and an increase in elongation at break from ⁇ 1% to ⁇ 2%). However, above a specific molecular weight, a saturation effect occurs. No considerable decrease of crystallinity and increase of mechanical properties is possible anymore (cf. Example 3).
  • the molecular weight M n is preferably adjusted to at least 9,000, preferably 10,000 to 100,000, more preferably 15,000 to 50,000 and most preferably 20,000 to 35,000 or Mw is preferably adjusted to 20,000 to 500,000, preferably 40,000 to 200,000 and more preferably 50,000 to 125,000.
  • melt viscosity correlates with the molecular weight of the polymer or copolymer as follows: the higher the molecular weight of a polymer or copolymer, the higher is also its melt viscosity. Therefore, for PAEK polymers or copolymers, melt viscosities in a range of 0.05-1.0 kN*s/m 2 , more preferably 0.15-0.6 kN*s/m 2 and particularly 0.2-0.45 kN*s/m 2 are preferred.
  • Ar 1 , Ar 2 and Ar 3 independently from each other denote unsubstituted or substituted, monocyclic or polycyclic aromatic hydrocarbons, wherein optional substituents may be selected from:
  • Rf 1 , Rf 2 , Rf 3 denote independently from each other C1 to C6 straight chain or branched chain or cyclic alkyl and alkoxy groups, and aryl groups, preferably Me, i-Pr, t-Bu, Ph, wherein each Ar 1 , Ar 2 and Ar 3 may have one or more Rf 1 , Rf 2 , Rf 3 substituent(s) respectively
  • a is a low integer which is more than 0, preferably lower than 12, more preferably 1 to 6 and particularly 1 to 3
  • b is a low integer which is more than 0, preferably lower than 12, more preferably 1 to 6 and particularly 1 to 3
  • c is 0 or a low integer, preferably lower than 12, more preferably 1 to 6 and particularly 1 to 3
  • n denotes the degree of polymerisation
  • the indices a, b and c denote the number of the respective units in squared brackets in the repeating unit of the polymer or the repeating units of the copolymer respectively, wherein one or more unit(s) of the same kind, e.g. the unit indexed with a, may be located between units of a different kind, e.g. the unit indexed with b and/or c.
  • the location of the respective units within the repeating unit may be derived from the abbreviation of the PAEK derivative.
  • PEK has a structure of the following formula
  • n denotes the degree of polymerisation.
  • the abbreviation PEEK indicates that two ester (E) units are followed by one ketone (K) unit, thus PEEK has a structure of the following formula
  • n denotes the degree of polymerisation.
  • the abbreviation PEKEKK indicates that one ester (E) unit is followed by one ketone (K) unit, then one ether unit follows which is followed by 2 ketone units, thus PEKEKK has a structure of the following formula
  • n denotes the degree of polymerisation
  • the degree of polymerisation n is preferably 10 to 1.000, more preferably 20 to 500 and particularly 40 to 250.
  • aromatic hydrocarbon groups Ar 1 , Ar 2 and Ar 3 are respectively and independently selected from the group consisting of 1,4-phenylene, 4,4′-biphenylene, 4,4′-isopropylidendiphenylene, 4,4′-diphenylsulfone, 1,4-, 1,5- and 2,6-naphthalene, 4,41-terphenylene and alpha-di(4-phenylene)phthalide.
  • the ratio between the amount of keto groups Y and the amount of ether- or thioether groups X is preferably 1:4 to 4:1. Within this ratio range, the crystallinity can be considerably lowered. For example, when comparing the use of PEK (ratio 1:1) and PEEK (ratio 2:1) having similar typical molecular weights (cf. examples 1 and 4), PEK is preferred over PEEK in terms of achieving lower crystallinity. On the other hand, a similarly controlled crystallinity can be achieved also when using PEEK by making use of other compensation control, e.g. by using PEEK of correspondingly higher molecular weight, or by appropriately predefining cooling after sintering at a high cooling rate.
  • a further possibility for tailoring the polymer to achieve the desirably limited final crystallinity of the manufactured object after the selective sintering process is to use an appropriate copolymer.
  • a copolymer with polyarylethersulfone (PAES) is preferable, in particular a polyaryletherketone(PAEK)/polyarylethersulfone(PAES)-diblock-copolymer or PAEK/PAES/PAEK-triblock-copolymer, more particular a polyetherketone(PEK)/polyethersulfone(PES)-diblock-copolymer or PEK/PES/PEK-triblock-copolymer.
  • the ratio of the amount of sulfone groups Z to the amount of keto groups Y is preferably between 50:50 and 10:90.
  • a glass transition temperature (T g ) and a melting point (T m ) of the polymer material can be adjusted which are suitable for processing the polymer in an apparatus for manufacturing a three-dimensional object by a selective sintering by means of electromagnetic radiation.
  • said PEK/PES-copolymers preferably have a T g higher than 180° C. and a melting temperature T m of 300 to 430° C.
  • end groups of the backbone chain of the polymer or copolymer may act as a crystallisation seed during the crystallisation. Therefore, the end groups of the polymer or copolymer may be derivatised in order to interfere with crystallisation, and thus to limit the crystallinity of the manufactured object.
  • the end groups may also be chosen such that they lead to an elongation of the polymer- or copolymer chain by a chemical reaction, preferably at temperatures above T m of the polymer, between the end group, e.g. by polycondensation, electrophilic or nucleophilic aromatic substitution, coupling reactions or the like. This results in a decrease of the crystallinity of the manufactured object due to an increased molecular mass
  • the end groups of the backbone chain of the polymer or copolymer depend on the kinds of monomers used for synthesis and on the kind of polymerisation. In the following, two different kinds of PAEK synthesis schemes resulting in different kinds of PAEKs with different end groups are shown.
  • PAEKs can be normally synthesized in two ways, namely by electrophilic aromatic substitution (Friedel-Crafts-Acylation) or nucleophilic aromatic substitution.
  • electrophilic aromatic substitution Frriedel-Crafts-Acylation
  • nucleophilic aromatic substitution for example, in the nucleophilic synthesis of a PAEK, a 1,4-bishydroxy-benzene is polymerized with an 4,4′ dihalogenated benzophenone component: x HO-Ph-OH+( y+ 1)Hal-Ph-CO-Ph-Hal ⁇ Hal-Ph-CO-Ph-[O-Ph-O] x [Ph-CO-Ph] y -Hal, wherein Hal is F, Cl, Br and x and y denote the number of monomers incorporated in the polymer.
  • the PAEK backbone chain in the above example PEEK may be terminated with a residual halogen group after the polymerization, most suitably with fluorine, optionally alternatively with chlorine or bromine, at none or one end (not shown) or at both ends (shown) of the backbone chain.
  • a residual halogen group after the polymerization, most suitably with fluorine, optionally alternatively with chlorine or bromine, at none or one end (not shown) or at both ends (shown) of the backbone chain.
  • PAES polyethersulfone
  • the aromatic bishydroxy-component may likewise be partly or fully substituted by a bisthiol component.
  • the halogen substituted ends of the polymer may be derivatized by a termination reaction with phenol: 2Ph-OH+Hal-Ph-CO-Ph-[O-Ph-O] x [Ph-CO-Ph] y -Hal ⁇ Ph-O-Ph-CO-Ph-[O-Ph-O] x [Ph-CO-Ph] y —O-Ph
  • Hal in the formulae above is F.
  • diacylaromates e.g. aromatic diacids or preferably aromatic diacid chlorides or aromatic diacid anhydrides, are polymerized with a bisaromatic ether or thioether component.
  • PEKK polymers or copolymers with phenyl groups at none or one end (not shown) or both ends (shown) of the backbone chain: x R A OC-Ph-COR A +( y+ 1)Ph-O-Ph ⁇ Ph-O-Ph-[OC-Ph-CO] x [Ph-O-Ph] y —H, wherein R A is Cl or —OH and x and y denote the number of monomers incorporated in the polymer.
  • the phenyl groups at the ends of the polymer may be derivatized by a termination reaction with benzoic acid chloride: 2Ph-COCl+Ph-O-Ph-[OC-Ph-CO] x [Ph-O-Ph] y —H ⁇ Ph-CO-Ph-O-Ph-[OC-Ph-CO] x [Ph-O-Ph] y —OC-Ph
  • the end groups may be preferably substituted, e.g. such that a PAEK polymer has the following formula: R T -U-[PAEK]-U-R T , wherein U is a linking moiety, for example NH, O, CO, CO—O—, SO, a single bond, —(CH 2 ) k wherein k is 1-6, or the like; and the left hand and right hand structural moieties R T may be the same or different structural groups, usually the structural moieties R T are the same.
  • R T is selected from the group of unsubstituted or substituted aliphatic or aromatic hydrocarbon residues.
  • U may be formed by direct reaction with the ends of the polymer or copolymer, for example a monofunctional hydroxy compound may form O as U, or it may be introduced as a substituent of the termination reagent, e.g. HO-Ph-COO-tert-butyl may form COO as U.
  • the polyaryletherketones with a halogenated end group can be terminated with ionic end groups like e.g. phenate salts like NaOPhSO 3 Na or NaOPhCOPhOPhSO 3 Na. Subsequent acidification of the phenate salts with e.g. HCl leads to —SO 3 H end groups that show a slightly reduced nucleation effect.
  • the polymer or copolymer may be blended with an alloying component in a blend, wherein a blend of at least two different polymers or copolymers is used. It is preferred that in such a blend, at least one component of the blend reduces the final crystallinity of the manufactured object.
  • the powder may be a composite powder which comprises one or more filler(s) and/or additive(s) besides a matrix of the respective polymer, copolymer or blend.
  • Fillers may be used to further improve the mechanical properties of the manufactured object.
  • fillers such as fibers, including but not limited to carbon fibers, glass fibers, Kevlar fibers, carbon nano fibers, or fillers having a low aspect ratio (glass beads, aluminum grit, etc.) or mineral fillers such as titane dioxide may be incorporated in the powder comprising at least one polymer or copolymer.
  • process additives which improve the proccessability of the powder e.g. free flowing agents such as the ones from the Aerosil series (e.g. Aerosil R974, Aerosil 200), or other functional additives, like heat stabilizers, oxidation stabilizers, color pigments (carbon black, graphite, etc.)) may be used.
  • the crystallinity of the manufactured object can be determined by various methods that are well known to the person skilled in the art.
  • the crystallinity can be determined based on Differential Scanning calorimetry (DSC) according to DIN 53765 which is used as a reference method according to the present invention.
  • DSC Differential Scanning calorimetry
  • Xc Melt ⁇ ⁇ enthalpy ⁇ ⁇ determined ⁇ ⁇ by ⁇ ⁇ DSC ⁇ [ J ⁇ / ⁇ g ] melt ⁇ ⁇ enthalpy ⁇ ⁇ 100 ⁇ % ⁇ ⁇ crystalline ⁇ ⁇ polymer ⁇ [ J ⁇ / ⁇ g ] ⁇ 100 ⁇ %
  • the crystallinity value relates to the polymer matrix of the composite which can also be calculated as defined above.
  • the crystallinity can also be determined by Wide Angle X-ray Scattering (WAXS) measurement.
  • WAXS Wide Angle X-ray Scattering
  • crystallinity was determined in the following Examples based on DSC measurements performed on a Mettler-Toledo DSC 823 according to DIN 53765.
  • the DSC sample was prepared from the middle of an ASTM D638 tensile bar that was built in x,y direction at least 5 cm from the edge of the exchangable frame on the laser sinter machine. Crystallinity was then determined by using the above shown formula.
  • the density was measured according to ISO 1183 on a Kern 770-60 balance with a Satorius Density Determination Set YDK 01.
  • Porosity ⁇ [ % ] Density ⁇ ⁇ of ⁇ ⁇ PAEK ⁇ ⁇ part ( ( ( d 100 ⁇ % - d 0 ⁇ % ) 100 ⁇ X c + d 0 ⁇ % ) ⁇ 100 ) - 100
  • the porosity can also be determined by micro-computerthomographie.
  • a useful device is e.g. the ⁇ -CT40 supplied by SCANCO Medical AG, Brüttisellen, Switzerland. The procedure is well known by the person skilled in the art.
  • melt viscosity are determined according to US-Patent 2006/0251878 A1 in a capillary viscosimeter with a wolfram-carbide nozzle at 400° C. and a shear rate of 1000 s ⁇ 1 .
  • the PEEK powder with a bulk density of 0.45 g/cm 3 was processed on a laser sintering machine of the type P700, that was modified by EOS for high temperature applications.
  • the temperature of the process chamber was 335° C.
  • the cooling rate was controlled by post-heating between 335° C. and Tg of PEEK (145° C.). The cooling rate showed a maximum average of 0.3° C./min
  • the parts showed the following properties:
  • the PEEK powder with a bulk density of 0.40 g/cm3 was processed on a laser sintering machine of the type P700, that was modified by EOS for high temperature applications.
  • the temperature of the process chamber was 335° C.
  • the cooling rate was controlled by post-heating between 335° C. and Tg of PEEK (145° C.). The cooling rate showed a maximum average of 0.3° C./min
  • the parts showed the following properties:
  • a powder made of PEEK (supplied by Victrex Plc, Thornton Cleveleys, Lancashire FY5 4QD, Great Britain) with a mean particle size distribution of 48 ⁇ m, wherein the PEEK polymer has a melt viscosity of 0.54 kN*s/m 2 , is thermally treated above glass transition temperature in an oven.
  • the PEEK powder was processed on a laser sintering machine of the type P700, that was modified by EOS for high temperature applications.
  • the temperature of the process chamber was 335° C.
  • the cooling rate was controlled by post-heating between 335° C. and Tg of PEEK (145° C.). The cooling rate showed a maximum average of 0.3° C./min
  • the parts showed the following properties:
  • the PEK powder was processed on a laser sintering machine of the type P700, that was modified by EOS for high temperature applications.
  • the temperature of the process chamber was 365° C.
  • the cooling rate was controlled by post-heating between 365° C. and Tg of PEK (157° C.). The cooling rate showed a maximum average of 0.3° C./min
  • the parts showed the following properties:
  • a powder made of PEK (supplied by Victrex Plc, Thornton Cleveleys, Lancashire FY5 4QD, Great Britain) with a mean particle size distribution of 48 ⁇ m, wherein the PEK polymer has a melt viscosity of 0.45 kN*s/m 2 , is thermally treated above glass transition temperature in an oven.
  • the PEK powder was processed on a laser sintering machine of the type P700, that was modified by EOS for high temperature applications.
  • the temperature of the process chamber was 365° C.
  • the cooling rate was controlled by post-heating between 365° C. and Tg of PEK (157° C.). The cooling rate showed a maximum average of 0.3° C./min
  • the parts showed the following properties:
  • a powder made of PEK (supplied by Victrex Plc, Thornton Cleveleys, Lancashire FY5 4QD, Great Britain) with a mean particle size distribution of 48 ⁇ m, wherein the PEK polymer has a melt viscosity of 0.45 kN*s/m 2 , is thermally treated above glass transition temperature in an oven.
  • the PEK powder was processed on a laser sintering machine of the type P700, that was modified by EOS for high temperature applications, as described in example 4.
  • the parts showed the following properties:

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Optics & Photonics (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Thermal Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
US12/454,473 2008-05-20 2009-05-18 Influencing specific mechanical properties of three-dimensional objects manufactured by a selective sintering by means of electromagnetic radiation from a powder comprising at least one polymer or copolymer Active 2029-12-02 US8420001B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US12/454,473 US8420001B2 (en) 2008-05-20 2009-05-18 Influencing specific mechanical properties of three-dimensional objects manufactured by a selective sintering by means of electromagnetic radiation from a powder comprising at least one polymer or copolymer

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
EP08009274.5A EP2123430B1 (fr) 2008-05-20 2008-05-20 Influences des propriétés mécaniques spécifiques d'objets tridimensionnels fabriqués par un frittage sélectif au moyen d'un rayonnement électromagnétique à partir d'une poudre comportant au moins un polymère ou copolymère
EP08009274.5 2008-05-20
EP08009274 2008-05-20
US18895808P 2008-08-14 2008-08-14
US12/454,473 US8420001B2 (en) 2008-05-20 2009-05-18 Influencing specific mechanical properties of three-dimensional objects manufactured by a selective sintering by means of electromagnetic radiation from a powder comprising at least one polymer or copolymer

Publications (2)

Publication Number Publication Date
US20090312454A1 US20090312454A1 (en) 2009-12-17
US8420001B2 true US8420001B2 (en) 2013-04-16

Family

ID=40040161

Family Applications (1)

Application Number Title Priority Date Filing Date
US12/454,473 Active 2029-12-02 US8420001B2 (en) 2008-05-20 2009-05-18 Influencing specific mechanical properties of three-dimensional objects manufactured by a selective sintering by means of electromagnetic radiation from a powder comprising at least one polymer or copolymer

Country Status (6)

Country Link
US (1) US8420001B2 (fr)
EP (2) EP3323601B1 (fr)
JP (1) JP5350884B2 (fr)
CN (1) CN101659119B (fr)
BR (1) BRPI0903385A2 (fr)
RU (1) RU2420403C2 (fr)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9587107B2 (en) 2010-09-27 2017-03-07 Arkema Inc. Heat treated polymer powders
US9931785B2 (en) 2013-03-15 2018-04-03 3D Systems, Inc. Chute for laser sintering systems
US9999924B2 (en) 2014-08-22 2018-06-19 Sigma Labs, Inc. Method and system for monitoring additive manufacturing processes
US10207489B2 (en) 2015-09-30 2019-02-19 Sigma Labs, Inc. Systems and methods for additive manufacturing operations
US10226817B2 (en) 2015-01-13 2019-03-12 Sigma Labs, Inc. Material qualification system and methodology
US10843401B2 (en) 2013-11-01 2020-11-24 Kraton Polymers U.S. Llc Fuse molded three dimensional article and a method for making the same
US11020895B2 (en) * 2018-07-05 2021-06-01 Lanzhou Institute Of Chemical Physics, Chinese Academy Of Sciences Direct-writing polyimide additive manufacturing material and preparation method thereof
US11267047B2 (en) 2015-01-13 2022-03-08 Sigma Labs, Inc. Material qualification system and methodology
US11478854B2 (en) 2014-11-18 2022-10-25 Sigma Labs, Inc. Multi-sensor quality inference and control for additive manufacturing processes
FR3146475A1 (fr) * 2023-03-10 2024-09-13 Arkema France Composition à base de polyaryléthercétone(s)
FR3146477A1 (fr) * 2023-03-10 2024-09-13 Arkema France Mélange de poudres

Families Citing this family (36)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102011078719A1 (de) * 2011-07-06 2013-01-10 Evonik Degussa Gmbh Pulver enthaltend mit Polymer beschichtete Partikel
JP2015500375A (ja) * 2011-12-12 2015-01-05 アドヴァンスド レーザー マテリアルズ，リミティド ライアビリティー カンパニーＡｄｖａｎｃｅｄ Ｌａｓｅｒ Ｍａｔｅｒｉａｌｓ，ＬＬＣ 前処理された材料を用いたレーザー焼結のための方法およびシステム
WO2013136096A1 (fr) * 2012-03-16 2013-09-19 University Of Exeter Fabrication additive
EP2746319B1 (fr) * 2012-12-21 2015-09-09 Materialise N.V. Procédé de fabrication d'objets par frittage sélectif
US20150024317A1 (en) * 2013-07-17 2015-01-22 Stratasys, Inc. High-Performance Consumable Materials for Electrophotography-Based Additive Manufacturing
US20160317542A1 (en) 2013-12-09 2016-11-03 Respira Therapeutics, Inc. Pde5 inhibitor powder formulations and methods relating thereto
GB2526243B (en) * 2014-02-24 2021-07-14 Victrex Mfg Ltd Polymeric materials
JP2017535643A (ja) 2014-11-03 2017-11-30 アーケマ・インコーポレイテッド ポリマーフレーク及び粉体の密度を高めるためのプロセス
US9695280B2 (en) * 2015-03-03 2017-07-04 Ricoh Co., Ltd. Methods for solid freeform fabrication
US20180236714A1 (en) * 2015-08-28 2018-08-23 Sabic Global Technologies B.V. Additive manufacturing products and processes
EP3365156B1 (fr) * 2015-10-22 2024-03-27 Dow Global Technologies LLC Procédé de fabrication additive par frittage sélectif et poudre utilisée à cet égard
WO2017116885A1 (fr) * 2015-12-28 2017-07-06 Arkema Inc. Prodédés de production de poudres polymères
WO2017173258A1 (fr) * 2016-04-01 2017-10-05 Arkema Inc. Structures de polymère fluoré imprimées en 3-d
US11248071B2 (en) 2016-04-01 2022-02-15 Arkema Inc. 3-D printed fluoropolymer structures
DE102016116372A1 (de) * 2016-09-01 2018-03-01 Fit Ag Mittels additiver Fertigung hergestelltes Bauteil mit einer Stützstruktur
US10875250B2 (en) * 2017-01-15 2020-12-29 Hexcel Corporation Method for analytically determining laser power for laser sintering
EP3521335B1 (fr) * 2017-02-06 2024-04-24 Solvay Specialty Polymers USA, LLC. Procédé de fabrication d'un objet tridimensionnel à l'aide de paek et de paes
JP7062675B2 (ja) * 2017-02-06 2022-05-06 ソルベイ スペシャルティ ポリマーズ ユーエスエー， エルエルシー Ｐａｅｋ及びｐａｅｓを使用して３次元物体を製造する方法
DE102017206963A1 (de) 2017-04-25 2018-10-25 Eos Gmbh Electro Optical Systems Verfahren zur Herstellung eines dreidimensionalen Objekts
WO2018217286A1 (fr) * 2017-05-23 2018-11-29 Huntington Ingalls Incorporated Système et procédé de traitement in situ de matériaux de fabrication additive et de constructions par fabrication additive
CN110730709B (zh) * 2017-06-07 2022-03-22 索尔维特殊聚合物美国有限责任公司 芳香族聚合物颗粒及其制备方法和用途
EP3415559A1 (fr) * 2017-06-13 2018-12-19 Lehmann & Voss & Co. KG Matériau composite et son utilisation dans des procédés de fabrication additive
US20200346399A1 (en) * 2018-01-18 2020-11-05 Arctic Biomaterials Oy Fiber-reinforced 3d printing
JP2019135092A (ja) * 2018-02-05 2019-08-15 株式会社リコー 立体造形物の製造方法、及び立体造形物の製造装置
DE102018206236A1 (de) 2018-04-23 2019-10-24 Eos Gmbh Electro Optical Systems Verfahren zum Herstellen eines mindestens ein Polymer umfassenden Pulvers sowie derartiges Pulver
EP3807090B1 (fr) * 2018-06-18 2024-01-24 Solvay Specialty Polymers USA, LLC. Procédé de fabrication d'un objet tridimensionnel utilisant un polymère poly(aryl ether sulfone) et un par(halo)fluoropolymère
CA3108297A1 (fr) * 2018-08-01 2020-02-06 Braskem America, Inc. Compositions thermoplastiques presentant une tenacite amelioree, articles fabriques a partir de celles-ci et procedes associes
JP7172463B2 (ja) * 2018-11-07 2022-11-16 株式会社リコー 立体造形用樹脂粉末、造形装置、及び造形方法
US12110363B2 (en) 2019-01-04 2024-10-08 Victrex Manufacturing Limited Polymeric material, manufacture and use
WO2020252224A1 (fr) * 2019-06-14 2020-12-17 3D Systems, Inc. Particules à base de polypropylène pour la fabrication additive
WO2021028240A1 (fr) * 2019-08-14 2021-02-18 Solvay Specialty Polymers Usa, Llc Procédé de fabrication additive pour fabriquer un objet tridimensionnel à l'aide d'un frittage laser sélectif
US11345082B2 (en) * 2019-09-23 2022-05-31 The Boeing Company Methods for additively manufacturing an object from a powder material
EP3825345A1 (fr) * 2019-11-19 2021-05-26 Arkema France Poudre améliorée pour une fabrication additive
JP7144703B2 (ja) * 2020-09-30 2022-09-30 ダイキン工業株式会社 三次元造形用組成物及び三次元造形物
KR20220049793A (ko) * 2020-10-15 2022-04-22 한화솔루션 주식회사 후공정을 통한 고기능성 고분자의 결정화 방법 및 이에 제조된 결정성 고분자
EP4352156A4 (fr) * 2021-05-14 2025-04-02 Braskem America, Inc. Polymères d'éthylène-ester vinylique de charge d'alimentation de fabrication additive

Citations (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6137419A (ja) 1984-07-31 1986-02-22 Sumitomo Bakelite Co Ltd 二軸配向熱可塑性ポリエ−テルエ−テルケトンフイルム
WO1989003301A1 (fr) 1987-10-15 1989-04-20 Mb Group Plc Procede de production de materiaux stratifies
WO1990006957A1 (fr) 1988-12-13 1990-06-28 E.I. Du Pont De Nemours And Company Feuille thermoformable en polyarylethercetone
JPH02250206A (ja) 1989-03-22 1990-10-08 Fujikura Ltd 絶縁電線およびこれを巻回したコイル
DE4410046C1 (de) 1994-03-23 1995-05-24 Eos Electro Optical Syst Verfahren und Material zum Herstellen eines dreidimensionalen Objekts durch Sintern
RU2048272C1 (ru) 1992-09-28 1995-11-20 Николай Константинович Толочко Устройство для изготовления трехмерных изделий из порошковых материалов
RU2080963C1 (ru) 1992-12-14 1997-06-10 Николай Константинович Толочко Способ изготовления трехмерных изделий из порошковых материалов
US6110411A (en) * 1997-03-18 2000-08-29 Clausen; Christian Henning Laser sinterable thermoplastic powder
US6136948A (en) 1992-11-23 2000-10-24 Dtm Corporation Sinterable semi-crystalline powder and near-fully dense article formed therewith
US6245281B1 (en) * 1997-10-27 2001-06-12 Huels Aktiengesellschaft Use of a nylon-12 for selective laser sintering
AU2003255225A1 (en) 2002-10-23 2004-05-13 Atofina Increase in the melting point and the enthalpy of melting of polyamides by a water treatment
JP2004137465A (ja) 2002-10-17 2004-05-13 Degussa Ag 選択的レーザー焼結のための焼結粉末、その製造方法、成形体の製造方法および成形体
US20040180980A1 (en) 2003-03-15 2004-09-16 Degussa Ag Laser-sintering powder with PMMI, PMMA, and/or PMMI-PMMA copolymers, process for its preparation, and moldings produced from this laser-sintering powder
US6932935B1 (en) * 1999-08-06 2005-08-23 Eos Gmbh Electro Optical Systems Method and device for producing a three-dimensional object
US20060134419A1 (en) 2004-12-21 2006-06-22 Degussa Ag Use of polyarylene ether ketone powder in a three-dimensional powder-based moldless production process, and moldings produced therefrom
WO2006092126A1 (fr) 2005-03-02 2006-09-08 STE Gesellschaft für Dichtungstechnik mbH Objet dote d'un revetement reduisant le frottement et procede de production de ce revetement
EP1707341A1 (fr) 2005-03-31 2006-10-04 3D Systems, Inc. Système de gestion thermique pour une chambre de production mobile pour l'utilisation avec une système de frittage par laser
US20060251878A1 (en) 2003-09-26 2006-11-09 Victrex Manufacturing Limited Polymeric material
US20070131609A1 (en) * 2005-12-08 2007-06-14 General Electric Company Membrane structure and method of making
US20070197692A1 (en) 2004-02-27 2007-08-23 Degussa Ag Polymer powder comprising a copolymer, use in a shaping method which uses a non-focused application of energy and moulded body that is produced from said polymer powder
US20070196561A1 (en) 2005-04-06 2007-08-23 Jochen Philippi Apparatus and method for the manufacture of a three- dimensional object
US20070232753A1 (en) * 2006-04-01 2007-10-04 Degussa Gmbh Polymer powder, process for production of and use of this powder, and resultant shaped articles
US20070267766A1 (en) 2004-03-21 2007-11-22 Toyota Motorsport Gmbh Powder for Rapid Prototyping and Associated Production Method
US7569174B2 (en) * 2004-12-07 2009-08-04 3D Systems, Inc. Controlled densification of fusible powders in laser sintering
US7575708B2 (en) * 2002-07-25 2009-08-18 The Boeing Company Direct manufacture of aerospace parts
US20090295042A1 (en) 2008-05-20 2009-12-03 Eos Gmbh Electro Optical Systems Selective sintering of structurally modified polymers
JP4502635B2 (ja) 2003-12-17 2010-07-14 インターナショナル・ビジネス・マシーンズ・コーポレーション 入力支援装置、メッセージ送信装置、およびプログラム

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0632978A (ja) * 1992-07-13 1994-02-08 Oiles Ind Co Ltd 摺動部材用ポリアミド樹脂組成物
JPH07331055A (ja) * 1994-06-02 1995-12-19 Mitsubishi Rayon Co Ltd ポリエーテルエーテルケトン樹脂組成物
GB0125618D0 (en) * 2001-10-24 2001-12-19 Victrex Mfg Ltd Polyaryletherketone polymer blends
DE102004012683A1 (de) * 2004-03-16 2005-10-06 Degussa Ag Lasersintern mit Lasern mit einer Wellenlänge von 100 bis 3000 nm
DE102004024440B4 (de) * 2004-05-14 2020-06-25 Evonik Operations Gmbh Polymerpulver mit Polyamid, Verwendung in einem formgebenden Verfahren und Formkörper, hergestellt aus diesem Polymerpulver

Patent Citations (36)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6137419A (ja) 1984-07-31 1986-02-22 Sumitomo Bakelite Co Ltd 二軸配向熱可塑性ポリエ−テルエ−テルケトンフイルム
RU2069154C1 (ru) 1987-10-15 1996-11-20 Карнауд Металбокс ПЛС Способ получения слоистого материала и устройство для его осуществления
WO1989003301A1 (fr) 1987-10-15 1989-04-20 Mb Group Plc Procede de production de materiaux stratifies
WO1990006957A1 (fr) 1988-12-13 1990-06-28 E.I. Du Pont De Nemours And Company Feuille thermoformable en polyarylethercetone
JPH04502635A (ja) 1988-12-13 1992-05-14 イー・アイ・デユポン・ドウ・ヌムール・アンド・カンパニー 熱成形できるポリアリールエーテルケトンシート
JPH02250206A (ja) 1989-03-22 1990-10-08 Fujikura Ltd 絶縁電線およびこれを巻回したコイル
RU2048272C1 (ru) 1992-09-28 1995-11-20 Николай Константинович Толочко Устройство для изготовления трехмерных изделий из порошковых материалов
US6136948A (en) 1992-11-23 2000-10-24 Dtm Corporation Sinterable semi-crystalline powder and near-fully dense article formed therewith
RU2080963C1 (ru) 1992-12-14 1997-06-10 Николай Константинович Толочко Способ изготовления трехмерных изделий из порошковых материалов
DE4410046C1 (de) 1994-03-23 1995-05-24 Eos Electro Optical Syst Verfahren und Material zum Herstellen eines dreidimensionalen Objekts durch Sintern
US6110411A (en) * 1997-03-18 2000-08-29 Clausen; Christian Henning Laser sinterable thermoplastic powder
US6245281B1 (en) * 1997-10-27 2001-06-12 Huels Aktiengesellschaft Use of a nylon-12 for selective laser sintering
US6932935B1 (en) * 1999-08-06 2005-08-23 Eos Gmbh Electro Optical Systems Method and device for producing a three-dimensional object
US7575708B2 (en) * 2002-07-25 2009-08-18 The Boeing Company Direct manufacture of aerospace parts
US20040102539A1 (en) 2002-10-17 2004-05-27 Degussa Ag Laser sintering powder with improved recycling properties, process for its production, and use of the laser sintering powder
JP2004137465A (ja) 2002-10-17 2004-05-13 Degussa Ag 選択的レーザー焼結のための焼結粉末、その製造方法、成形体の製造方法および成形体
AU2003255225A1 (en) 2002-10-23 2004-05-13 Atofina Increase in the melting point and the enthalpy of melting of polyamides by a water treatment
US20040180980A1 (en) 2003-03-15 2004-09-16 Degussa Ag Laser-sintering powder with PMMI, PMMA, and/or PMMI-PMMA copolymers, process for its preparation, and moldings produced from this laser-sintering powder
US20060251878A1 (en) 2003-09-26 2006-11-09 Victrex Manufacturing Limited Polymeric material
JP4502635B2 (ja) 2003-12-17 2010-07-14 インターナショナル・ビジネス・マシーンズ・コーポレーション 入力支援装置、メッセージ送信装置、およびプログラム
US20070197692A1 (en) 2004-02-27 2007-08-23 Degussa Ag Polymer powder comprising a copolymer, use in a shaping method which uses a non-focused application of energy and moulded body that is produced from said polymer powder
JP2007535585A (ja) 2004-03-21 2007-12-06 トヨタ モータースポーツ ゲーエムベーハー ラピッドプロトタイピング用粉末およびその製造方法
US20070267766A1 (en) 2004-03-21 2007-11-22 Toyota Motorsport Gmbh Powder for Rapid Prototyping and Associated Production Method
US7569174B2 (en) * 2004-12-07 2009-08-04 3D Systems, Inc. Controlled densification of fusible powders in laser sintering
EP1674497A1 (fr) 2004-12-21 2006-06-28 Degussa AG Utilisation d'une poudre de polyarylèneéthercétone dans un procédé de fabrication tridimensionnel à base de poudre n'impliquant pas d'outil et les pièces moulées ainsi produites
JP2007039631A (ja) 2004-12-21 2007-02-15 Degussa Ag 三次元の粉末をベースとする型を使用しない製造方法におけるポリアリーレンエーテルケトン粉末の使用およびこれから製造される成形体
US20060134419A1 (en) 2004-12-21 2006-06-22 Degussa Ag Use of polyarylene ether ketone powder in a three-dimensional powder-based moldless production process, and moldings produced therefrom
US20080247687A1 (en) 2005-03-02 2008-10-09 Christoph Stecher Object Comprising a Friction-reducing Coating, and Method for the Production of a Coating
WO2006092126A1 (fr) 2005-03-02 2006-09-08 STE Gesellschaft für Dichtungstechnik mbH Objet dote d'un revetement reduisant le frottement et procede de production de ce revetement
JP2006312310A (ja) 2005-03-31 2006-11-16 Three D Syst Inc レーザ焼結システムに使用するための取外し可能な構築チャンバのための温度管理システム
EP1707341A1 (fr) 2005-03-31 2006-10-04 3D Systems, Inc. Système de gestion thermique pour une chambre de production mobile pour l'utilisation avec une système de frittage par laser
US20070196561A1 (en) 2005-04-06 2007-08-23 Jochen Philippi Apparatus and method for the manufacture of a three- dimensional object
US20070131609A1 (en) * 2005-12-08 2007-06-14 General Electric Company Membrane structure and method of making
US20070232753A1 (en) * 2006-04-01 2007-10-04 Degussa Gmbh Polymer powder, process for production of and use of this powder, and resultant shaped articles
US20090295042A1 (en) 2008-05-20 2009-12-03 Eos Gmbh Electro Optical Systems Selective sintering of structurally modified polymers
JP2010006057A (ja) 2008-05-20 2010-01-14 Eos Gmbh Electro Optical Systems 構造修飾されたポリマーの選択的焼結

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
Dawson, et al., X-ray data for poly(aryl ether ketones), Polymer, 1980, vol. 21, May, pp. 577-578.
DIN 53765 "Testing of plastics and elastomeres, Thermal analysis, DSC-method", Mar. 1994, Beuth Verlag.
DIN-EN ISO 1183-1, Plastics "Methods for determining the density of non-cellular plastics" Part 1-Immersion method, liquid pyknometer method and titration method; (ISO 1183-1: 2004) German Version; (EN ISO 1183-1: 2004) English Version, Beuth Verlag.
Salmoria at al., "Rapid manufacturing of PA/HDPE blend specimens by selective laster sintering: Microstructural characterization", ScienceDirect, Polymer Testing 26 (2007) 361-368.

Cited By (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9587107B2 (en) 2010-09-27 2017-03-07 Arkema Inc. Heat treated polymer powders
US12180360B2 (en) 2010-09-27 2024-12-31 Arkema Inc. Heat treated polymer powders
US11046847B2 (en) 2010-09-27 2021-06-29 Arkema, Inc. Heat treated polymer powders
US9931785B2 (en) 2013-03-15 2018-04-03 3D Systems, Inc. Chute for laser sintering systems
US12145317B2 (en) 2013-03-15 2024-11-19 3D Systems, Inc. Powder distribution for laser sintering systems
US11396134B2 (en) 2013-03-15 2022-07-26 3D Systems, Inc. Powder distribution for laser sintering systems
US10843401B2 (en) 2013-11-01 2020-11-24 Kraton Polymers U.S. Llc Fuse molded three dimensional article and a method for making the same
US9999924B2 (en) 2014-08-22 2018-06-19 Sigma Labs, Inc. Method and system for monitoring additive manufacturing processes
US12172371B2 (en) 2014-08-22 2024-12-24 Divergent Technologies, Inc. Defect detection for additive manufacturing systems
US11858207B2 (en) 2014-08-22 2024-01-02 Sigma Additive Solutions, Inc. Defect detection for additive manufacturing systems
US11135654B2 (en) 2014-08-22 2021-10-05 Sigma Labs, Inc. Method and system for monitoring additive manufacturing processes
US11607875B2 (en) 2014-08-22 2023-03-21 Sigma Additive Solutions, Inc. Method and system for monitoring additive manufacturing processes
US11478854B2 (en) 2014-11-18 2022-10-25 Sigma Labs, Inc. Multi-sensor quality inference and control for additive manufacturing processes
US12296533B2 (en) 2014-11-18 2025-05-13 Divergent Technologies, Inc. Multi-sensor quality inference and control for additive manufacturing processes
US11931956B2 (en) 2014-11-18 2024-03-19 Divergent Technologies, Inc. Multi-sensor quality inference and control for additive manufacturing processes
US11267047B2 (en) 2015-01-13 2022-03-08 Sigma Labs, Inc. Material qualification system and methodology
US10226817B2 (en) 2015-01-13 2019-03-12 Sigma Labs, Inc. Material qualification system and methodology
US10717264B2 (en) 2015-09-30 2020-07-21 Sigma Labs, Inc. Systems and methods for additive manufacturing operations
US12019026B2 (en) 2015-09-30 2024-06-25 Divergent Technologies, Inc. Systems and methods for additive manufacturing operations
US10207489B2 (en) 2015-09-30 2019-02-19 Sigma Labs, Inc. Systems and methods for additive manufacturing operations
US12292384B2 (en) 2015-09-30 2025-05-06 Divergent Technologies, Inc. Systems and methods for additive manufacturing operations
US11674904B2 (en) 2015-09-30 2023-06-13 Sigma Additive Solutions, Inc. Systems and methods for additive manufacturing operations
US11020895B2 (en) * 2018-07-05 2021-06-01 Lanzhou Institute Of Chemical Physics, Chinese Academy Of Sciences Direct-writing polyimide additive manufacturing material and preparation method thereof
FR3146475A1 (fr) * 2023-03-10 2024-09-13 Arkema France Composition à base de polyaryléthercétone(s)
FR3146477A1 (fr) * 2023-03-10 2024-09-13 Arkema France Mélange de poudres
WO2024188726A1 (fr) * 2023-03-10 2024-09-19 Arkema France Composition à base de polyaryléthercétone(s)
WO2024188725A1 (fr) * 2023-03-10 2024-09-19 Arkema France Mélange de poudres

Also Published As

Publication number Publication date
BRPI0903385A2 (pt) 2010-07-20
EP3323601A3 (fr) 2018-08-15
HK1139361A1 (zh) 2010-09-17
RU2009118967A (ru) 2010-11-27
JP5350884B2 (ja) 2013-11-27
CN101659119A (zh) 2010-03-03
EP3323601B1 (fr) 2022-04-27
CN101659119B (zh) 2016-01-20
JP2010007052A (ja) 2010-01-14
US20090312454A1 (en) 2009-12-17
EP2123430B1 (fr) 2020-07-01
EP2123430A1 (fr) 2009-11-25
EP3323601A2 (fr) 2018-05-23
RU2420403C2 (ru) 2011-06-10

Similar Documents

Publication Publication Date Title
US8420001B2 (en) Influencing specific mechanical properties of three-dimensional objects manufactured by a selective sintering by means of electromagnetic radiation from a powder comprising at least one polymer or copolymer
US9895842B2 (en) Selective sintering of structurally modified polymers
CN106029344B (zh) 聚合材料
CN101623929A (zh) 结构改性聚合物的选择性烧结
US10807302B2 (en) Semi-crystalline build materials
US20190106569A1 (en) Semi-crystalline build materials
CN110545941A (zh) 用于选择性激光烧结的系统
HK1139361B (en) A method for influencing specific mechanical properties of three-dimensional objects manufactured from a powder
HK1209695B (en) Selective sintering of structurally modified polymers
HK1135066B (en) Selective sintering of structurally modified polymers

Legal Events

Date Code Title Description
AS Assignment

Owner name: EOS GMBH ELECTRO OPTICAL SYSTEMS, GERMANY

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:LEUTERER, MARTIN;PFISTER, ANDREAS;MUELLER, FRANK;AND OTHERS;SIGNING DATES FROM 20090722 TO 20090807;REEL/FRAME:023138/0191

FEPP Fee payment procedure

Free format text: PAYOR NUMBER ASSIGNED (ORIGINAL EVENT CODE: ASPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

STCF Information on status: patent grant

Free format text: PATENTED CASE

FPAY Fee payment

Year of fee payment: 4

MAFP Maintenance fee payment

Free format text: PAYMENT OF MAINTENANCE FEE, 8TH YEAR, LARGE ENTITY (ORIGINAL EVENT CODE: M1552); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

Year of fee payment: 8

FEPP Fee payment procedure

Free format text: MAINTENANCE FEE REMINDER MAILED (ORIGINAL EVENT CODE: REM.); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

FEPP Fee payment procedure

Free format text: 11.5 YR SURCHARGE- LATE PMT W/IN 6 MO, LARGE ENTITY (ORIGINAL EVENT CODE: M1556); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

MAFP Maintenance fee payment

Free format text: PAYMENT OF MAINTENANCE FEE, 12TH YEAR, LARGE ENTITY (ORIGINAL EVENT CODE: M1553); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

Year of fee payment: 12